Novel Thione-Thiol Rearrangement of Dithiocarbonic Acid O-(2,2,6,6-Tetramethylpiperidin-1-yl) Ester in the Context of Controlled Radical Polymerization

Peter Nesvadba; Lucienne Bugnon; Trixie Wagner

doi:10.2533/chimia.2010.56

Novel Thione-Thiol Rearrangement of Dithiocarbonic Acid O-(2,2,6,6-Tetramethylpiperidin-1-yl) Ester in the Context of Controlled Radical Polymerization

Authors

Peter Nesvadba Ciba Inc. (now part of BASF), Performance Chemicals Research, R-1059.6.05, Klybeckstr. 141, CH-4002 Basel;, Email: peter.nesvadba@basf.com
Lucienne Bugnon Ciba Inc. (now part of BASF), Performance Chemicals Research, R-1059.6.05, Klybeckstr. 141, CH-4002 Basel
Trixie Wagner Novartis Institutes for BioMedical Research, Lichtstrasse 35, CH-4056 Basel

DOI:

https://doi.org/10.2533/chimia.2010.56

Keywords:

Acyloxyamines, Alkoxyamines, Controlled/living radical polymerization, Newman-kwart rearrangement, Nitroxides, Thione-thiol rearrangement, Thionitroxides

Abstract

Addition of the lithium salt of N-hydroxy-2,2,6,6-tetramethylpiperidine 10 to carbon disulfide and subsequent methylation affords the rearranged dithiocarbonic acid S-methyl-S'-(2,2,6,6-tetramethylpiperidin-1-yl)-ester 9 rather than the expected xanthate ester S-methyl-O'-(2,2,6,6-tetramethylpiperidin-1-yl)-ester 8. n-Butylacrylate could be polymerized with the novel compound 9 even though the polymerization was not controlled.